Method and apparatus for producing chlorine gas in an electrolytic cell

Abstract

The nanobubble generator is 1 cm 3 At least 10 per 6 A method and apparatus for producing chlorine gas is disclosed in which nanobubbles are introduced into an electrolytic cell containing a pair of electrodes and a chlorine-containing electrolytic liquid at a concentration of nanobubbles, and the electrolytic cell is operated to produce chlorine gas. TIFF2025502967000002.tif138128

Description

[Technical field]

[0001] Claiming priority This application claims priority to U.S. Provisional Patent Application No. 63 / 299,765, filed January 14, 2022, the entire contents of which are incorporated herein by reference.

[0002] Technical Field The present invention relates to the production of chlorine gas in an electrolytic cell. [Background technology]

[0003] background In the fields of chemistry and manufacturing, electrolysis is a technique that uses direct current (DC) to drive non-spontaneous chemical reactions. Electrolysis is used as a step in the separation of elements from naturally occurring sources such as ores using electrolytic cells. An electrolytic cell contains a pair of electrodes and a liquid electrolyte, typically water. When activated, the cell electrolyzes the liquid to drive non-spontaneous chemical reactions. The voltage required for electrolysis to occur is called the decomposition potential. The etymology of the word electrolysis comes from "lysis," to separate or destroy, and "electric," to bear electricity, and thus electrolysis means "through an electrical breakdown."

[0004] During electrolysis, bubbles can form at the electrodes. Although not present in high concentrations, these bubbles are considered undesirable because they can block the electrode surface and ion conduction pathways, which leads to reduced efficiency of the electrolytic cell. See Argulo et al., "Influence of Bubbles on the Energy Conversion Efficiency of Electrochemical Reactors," Joule, 4(3):555-579 (March 18, 2020). Several approaches have been proposed to address this issue by promoting bubble detachment, including modifying the electrode surface, adjusting the composition of the electrolyte, inducing flow in the electrolyte, and applying electromagnetic or ultrasonic energy to the electrolytic cell. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Argulo et al., "Influence of Bubbles on the Energy Conversion Efficiency of Electrochemical Reactors," Joule, 4(3):555-579 (March 18, 2020) Summary of the Invention

[0006] overview The inventors have discovered that the introduction of high concentrations of nanobubbles into an electrolytic cell dramatically increases the efficiency of oxidant production, including chlorine, hypochlorous acid, or other free and available chlorine (FAC), such as hydrogen peroxide, chlorine dioxide, ozone, peroxydisulfate, and / or other mixed oxidants. The presence of high concentrations of nanobubbles can enhance the electrolysis process to more efficiently generate chlorine gas from saltwater or other liquids. Without being bound by theory, it is believed that the presence of high concentrations of nanobubbles increases the charge density in the volume of the electrolytic liquid, thereby spatially expanding the area subject to the effect of the electric potential. High concentrations of nanobubbles also increase the interaction between the electrodes and the electrolyte. As a result, electrical resistance is reduced and the amount of energy required to generate chlorine gas (or dissolved form) is reduced, thereby reducing overall costs.

[0007] The addition of nanobubbles to an electrolytic liquid (e.g., feed electrolyte) allows for an enhancement of the ion mobility and kinetics of the electrolytic liquid, which leads to an increase in the efficiency of the formation of oxidants, hydrogen, oxygen, and affects the rate of scaling and precipitation of dissolved salts. The addition and properties of nanobubbles can preferentially adjust the ion mobility, increase the availability of certain ions involved in the electrochemical process, and enhance the performance of the electromotive force (EMF) applied to the electrodes in contact with the feed electrolyte. The electrolytic liquid can enhance the performance of the electrolytic process by increasing the production of oxidants and hydrogen gas, reducing the required energy input, and / or extending the operating time, without compromising the efficiency of the components of the system (e.g., those caused by the effects of electrode scaling and corrosion).

[0008] Thus, in a first aspect, a method for producing chlorine gas is described, comprising the steps of: (a) dissolving 1 cm 3 At least 10 per 6(b) introducing nanobubbles from a nanobubble generator into an electrolytic cell comprising a pair of electrodes and a chlorine-containing electrolyte liquid at a concentration of 1 nanobubble cm; and (b) operating the electrolytic cell to produce chlorine gas. In some embodiments, the nanobubble concentration is greater than or equal to 1 cm. 3 At least 10 per 6 Nanobubbles, 1 cm 3 At least 10 per 7 Nanobubbles, 1 cm 3 At least 10 per 8 Nanobubbles, 1 cm 3 At least 10 per 9 nanobubbles, or 1 cm 3 At least 10 per 10 These are nanobubbles.

[0009] The nanobubble concentration is 1 cm 3 It is expressed as nanobubbles per nanobubble. It is measured by collecting three samples from the electrolytic cell (which receives the outflow from the nanobubble generator) and analyzing each sample within 20 minutes of acquisition by nanoparticle tracking analysis using a Nanosight NS3000 analyzer available from Malvern PANalytical. Each sample is filtered using a 0.45 μm filter before analysis using the Nanosight NS3000 analyzer.

[0010] The nanobubble generator may be located within the electrolytic cell (e.g., immersed in the electrolytic liquid) or may be located outside the electrolytic cell (e.g., as a separate module in fluid communication with the electrolytic cell). In some embodiments, the nanobubble generator and the electrolytic cell are located within a common housing.

[0011] In some embodiments, the method further comprises extracting chlorine gas from the electrolytic cell as the chlorine gas is produced or after a predetermined time.

[0012] In some embodiments, the electrolyzer further produces oxygen gas, which can be extracted from the electrolyzer as it is produced or after a predetermined time. In some embodiments, the electrolyzer further produces hypochlorous acid or other oxidants, including one or more of free and available chlorine (FAC), hydrogen peroxide, chlorine dioxide, ozone, peroxydisulfate, and / or mixed oxidants, and hydrogen gas.

[0013] The nanobubbles are filled with a gas. In some embodiments, the gas is air, nitrogen, carbon dioxide, NO X , methane, and combinations thereof.

[0014] The chlorine-containing electrolytic liquid may include water, salt water, ammonia, wastewater, industrial solutions, aqueous sodium chloride solutions (brine solutions), or combinations thereof. The liquid may contain salt. As used herein, "wastewater" includes, but is not limited to, municipal wastewater, industrial wastewater, storm water, sewage, grey water, treated water from fermentation or mining processes, or combinations thereof. In some embodiments, the wastewater includes ammonia. The use of wastewater as the electrolytic liquid provides a convenient means for wastewater treatment to remove contaminants. As used herein, salt water includes, but is not limited to, naturally occurring salt water, such as seawater, water for use in salt water pools or spas, or other sources. The use of salt water as the electrolytic liquid provides a convenient means for decomposing NaCl to produce chlorine for use in desalination plants, pool and spa systems, and other industrial processes.

[0015] The devices and methods provided herein can produce electrolysis products including potassium, sodium metal, and chemicals such as bleach, chlorine, bromine, sodium hydroxide, sodium chlorate, hydrogen, oxygen, aluminum, copper, magnesium, zinc, adiponitrile, and combinations thereof. Additionally, the methods provided herein can be applied to salt water chlorination, a process of chlorinating swimming pools and hot tubs with dissolved salts (e.g., 1000-36,000 ppm or 1-36 g / L salt). The methods herein can include the use of chlorine generators (also known as salt baths, salt generators, salt chlorinators, or SWGs) that use electrolysis in the presence of dissolved salts to produce chlorine gas or its dissolved forms, such as hypochlorous acid and sodium hypochlorite, which have previously been used as purifying agents in pools. Hydrogen can also be produced as a by-product.

[0016] The nanobubble generator may have a variety of configurations and may utilize a variety of means for generating nanobubbles. In one embodiment, the nanobubble generator includes: (a) an elongated housing having a first end and a second end, the housing defining a liquid inlet, a liquid outlet, and an internal cavity adapted to receive a liquid carrier from a liquid source; (b) a gas permeable member disposed at least partially within the internal cavity of the housing, the gas permeable member having an open end adapted to receive pressurized gas from a gas source, a closed end, and a porous sidewall extending between the open and closed ends, and defining an inner surface, an outer surface, and a lumen. The housing and the gas permeable member are configured such that when the liquid carrier from the liquid source flows parallel to the outer surface of the gas permeable member from the liquid inlet to the liquid outlet, the flow velocity of the liquid carrier is greater than a turbulence threshold at which the liquid creates a turbulent flow condition, thereby allowing the liquid to shear the gas from the outer surface of the gas permeable member to form nanobubbles in the liquid carrier. For example, the housing and gas permeable member may be configured to generate a flow velocity of at least 2 m / s. This generator is described in U.S. Patent Nos. 10,591,231 and 10,598,447, each entitled "Compositions Containing Nano-Bubbles in a Liquid Carrier," which are assigned to the same assignee as the present application and are incorporated by reference in their entireties.

[0017] The nanobubble generator, as described in USSN 63 / 150,973, "Nano-Bubble Generator," filed February 18, 2021, which is assigned to the same assignee as the present application and is incorporated herein by reference in its entirety, may further include at least one electrical conductor adapted to generate a magnetic flux parallel to the outer surface of the gas permeable member (which may be electrically conductive) as the liquid carrier flows from the liquid inlet to the liquid outlet. In some embodiments, the electrical conductor is in the form of an electromagnetic coil. In some embodiments, the nanobubble generator may include a helical member adapted to rotate the liquid carrier as the liquid carrier flows from the liquid inlet to the liquid outlet. The helical member may, in some embodiments, include an electromagnetic coil adapted to generate a magnetic flux parallel to the outer surface of the gas permeable member as the liquid carrier flows from the liquid inlet to the liquid outlet. In some embodiments, the nanobubble generator further comprises a hydrofoil located within the interior cavity of the housing.

[0018] Another example of a nanobubble generator, also described in USSN 63 / 150,973, includes: (a) an elongated housing including a first end and a second end, the elongated housing further including an internal cavity and a gas inlet adapted to introduce pressurized gas from a gas source into the internal cavity; (b) a gas permeable member disposed at least partially within the internal cavity of the housing, the gas permeable member including a liquid inlet adapted to receive liquid from a liquid source, a liquid outlet, and a porous sidewall extending between the liquid inlet and the liquid outlet, the gas permeable member defining an inner surface, an outer surface, and a lumen through which the liquid flows; and (c) at least one electrical conductor adapted to generate a magnetic flux parallel to an inner surface of the gas permeable member as the liquid carrier flows from the liquid inlet to the liquid outlet. The housing and gas permeable member are configured such that as the liquid carrier from the liquid source flows parallel to the inner surface of the gas permeable member from the liquid inlet to the liquid outlet, the flow velocity of the liquid carrier is greater than a turbulence threshold at which the liquid creates a turbulent flow condition, thereby allowing the liquid to shear gas from the inner surface of the gas permeable member to form nanobubbles in the liquid carrier.

[0019] Another example of a suitable nanobubble generator is described in USSN 16 / 818,217, "Submersible Non-Bubble Generating Device and Method," filed March 13, 2020, which is assigned to the same assignee as the present application and is incorporated herein by reference in its entirety. The nanobubble generator includes: (a) a motor having a rotatable shaft; (b) a pivotable permeable member including a body having a wall and a plurality of pores through which gas introduced into the pivotable permeable member can flow, the pivotable permeable member being connectable to a gas inlet configured to introduce gas from a gas source into the pivotable permeable member, the pivotable permeable member being connected to the rotatable shaft of the motor and adapted to rotate with the rotatable shaft; and (c) a rotatable tube support including an elongated body having a wall and defining an internal cavity. The wall defines a plurality of perforations. The internal cavity of the rotatable tube support is configured to house the pivotable permeable member. The rotatable tube support is coupled to and rotatable with a rotatable shaft of the motor. The rotatable tube support is adapted, upon rotation, to introduce liquid into an interior cavity of the rotatable tube support and to move the liquid away from an outer surface of the body of the rotatable permeable member. The pivotable permeable member is adapted, upon rotation, to simulate turbulence in the liquid above a turbulence threshold, which turbulence allows the liquid to shear gas from the outer surface of the pivotable permeable member, thereby forming nanobubbles in the liquid.

[0020] An apparatus for generating chlorine gas is also described, comprising: (a) a 1 cm 3 At least 10 per 6 (b) a nanobubble generator capable of generating nanobubbles; and (b) an electrolytic cell in communication with the nanobubble generator, the electrolytic cell comprising a pair of electrodes. The electrolytic cell is capable of generating chlorine gas from a chlorine-containing electrolytic liquid. The nanobubble concentration is determined as described above.

[0021] The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will become apparent from the description and drawings, and from the appended claims. [Brief description of the drawings]

[0022] [Figure 1] FIG. 1 is a schematic diagram of one embodiment of a method and apparatus for producing chlorine gas according to the present invention. [Diagram 2] FIG. 1 is a schematic diagram of an exemplary apparatus for generating a composition comprising nanobubbles dispersed in a liquid carrier. [Diagram 3] FIG. 2 is an exploded perspective view of a second exemplary apparatus for producing a composition comprising nanobubbles dispersed in a liquid carrier. [Figure 4A] FIG. 2 is a top view of a third exemplary apparatus for producing a composition comprising nanobubbles dispersed in a liquid carrier. [Figure 4B] FIG. 4B is a side cross-sectional view of the device of FIG. 4A. [Figure 4C] FIG. 4B is an exploded view of the device of FIG. 4A. [Diagram 5] FIG. 1 is a schematic diagram of an exemplary apparatus for generating a composition comprising nanobubbles dispersed in a liquid carrier. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] Detailed Description Referring to FIG. 1, a chlorine gas generation system 100 is shown that includes a nanobubble generator 102 in communication with an electrolytic cell 104. As shown in FIG. 1, the nanobubble generator 102 and the electrolytic cell 104 are separate modules contained within a common housing 110. However, in some embodiments, the nanobubble generator may be contained (e.g., submerged) in the electrolyte 105 of the cell 104. In other embodiments, the electrolytic cell may be contained within the nanobubble generator. In yet other embodiments, the nanobubble generator and the electrolytic cell are separate modules, but are not contained within a common housing.

[0024] To create nanobubbles, a source of gas 101 and a source of chlorine-containing liquid 107 are fed into a nanobubble generator 102. Examples of suitable gases include air, nitrogen, carbon dioxide, NO X , methane, and combinations thereof. The choice of gas depends on the end use of the chlorine gas generation system. The liquid 107 is typically an aqueous liquid. If the system 100 is incorporated into a wastewater treatment plant, the liquid 107 may be wastewater. If the system 100 is incorporated into a desalination plant or a salt water pool or spa system, the liquid 107 may be salt water. The liquid 107 may then contain other dissolved components, such as ammonia.

[0025] The nanobubble generator 102 produces a composition 103 containing a high concentration of nanobubbles dispersed in a liquid carrier, which is then introduced into an electrolytic bath 104. The concentration of nanobubbles is about 1 cm 3 At least 10 per 6 Nanobubbles, 1 cm 3 At least 10 per 7 Nanobubbles, 1 cm 3 At least 10 per 8 Nanobubbles, 1 cm 3 At least 10 per 9 nanobubbles, or 1 cm 3 At least 10 per 101 nanobubbles. As explained in the overview above, introducing a high concentration of nanobubbles into the electrolytic cell increases the efficiency of chlorine gas production. The cell 104 includes an anode 106a and a cathode 106b. The cell 104 reduces chlorine in the chlorine-containing liquid carrier to chlorine gas at the cathode 106b. The chlorine gas thus produced may be introduced into a chlorine application 112 via line 109. The chlorine application 112 may be a swimming pool, a saltwater pool, a hot tub, a water treatment vessel, a chloralkali process, or any other suitable application. The chlorine gas may be extracted as it is produced. Alternatively, the chlorine gas may remain stored in the cell 104 and be extracted when desired. In some embodiments, the chlorine gas may be released into a chlorine application 112 incorporating a common housing 110 and / or cell 104.

[0026] Oxidation occurs at the anode 106a of the vessel 104. If the liquid carrier is an aqueous carrier, oxidation of the carrier generates oxygen gas at the anode 106a. The oxygen gas may be recycled via line 108 and used as a gas source for forming nanobubbles. Alternatively, oxygen gas may be supplied to the chlorine application 112.

[0027] Under normal circumstances (i.e., when nanobubbles are not added to the feed electrolyte prior to entering the electrolytic cell 104), the formation of gas bubbles at the boundary layer between the electrodes (anode 106a and cathode 106b) and the feed electrolyte can reduce the availability of available area on the surfaces of the electrodes (anode 106a and cathode 106b) in contact with the fluid, reducing the production of oxidant and hydrogen. Thus, the normal electrolysis process has a reduced level of efficiency (conversion of electrical power to oxidant production) for producing oxidant and hydrogen gas.

[0028] In contrast, the apparatus and methods provided herein include electrochemical processes enhanced with nanobubbles, which have more efficient ion mobility. When continuously introduced into the feed electrolyte, the nanobubbles can act as catalysts in reactions leading to the production of oxidants and hydrogen gas. The nanobubbles can act as reactants when the density of the nanobubbles decreases over the time of the reaction, e.g., when the nanobubbles are consumed in the process.

[0029] The feed electrolyte can include one or more dissolved salts, such as alkali metal based salts (Li+, Na+, K+, Rb+, Cs+, etc.), alkaline earth based salts (e.g., Mg++, Ca++), or transition metal based cations (e.g., Cr, Fe, Co, Ni, Cu, Zn, etc.), in various combinations and concentrations, and optionally with a mixture of counter ions, and any suitable anion components, including but not limited to F-, Cl-, Br-, I-, PO4-, SO4-, and nitrogen based anions.

[0030] The composition and conductivity of the feed electrolyte can be adjusted through modification of the concentration and valency of the dissolved salts, the temperature, and the pH of the feed solution. An oscillating magnetic field can optionally be applied at variable frequencies during nanobubble generation.

[0031] A variety of nanobubble generators may be used to generate nanobubble-containing compositions. One embodiment, shown in FIG. 2 and described in the aforementioned U.S. Patents 10,591,231 and 10,598,447, features an exemplary device 10 that includes a housing 12 of cylindrical configuration. A porous, gas-permeable ceramic tube 20 spans between end walls 22 of the housing 12 and is rigidly supported at both ends. A sealing structure 24 including an O-ring is provided between the tube 20 and the end walls 22.

[0032] There is an inlet to the housing at 26 and an outlet from the housing at 28. A pump 30 is connected to the inlet 26 and there is a pressure regulator 32 between the pump 30 and the inlet 26. A jet pump 34 and a pressure gauge 36 are connected to the outlet 28. A source of gas under pressure 38 is connected to an inlet 44 to the tube 20 via a pressure regulator 40, a flow meter 42, and / or a sealing structure 24. It is noted that the tube 20 is closed at the end opposite the inlet 44. It is noted that the tube 20 is closed at the end opposite the inlet 44. The device 10 may optionally include a helical member 46, which protrudes into the flowing liquid and enhances the turbulence caused by the position of the inlet. The device is configured to generate a flow above a turbulence threshold, for example a flow velocity of at least 2 m / s. Turbulence above the turbulence threshold serves two functions: (a) to shear nascent bubbles away from the surface of tube 120, and (b) to remove newly formed bubbles from near the surface of tube 120. Turbulence within housing 12 of device 10 accomplishes both of these goals.

[0033] A second embodiment of a suitable nanobubble generator, particularly useful in systems in which the nanobubble generator is submerged in an electrolytic bath, is shown in Figure 3 and is also described in the aforementioned USSN 16 / 818,217, which is incorporated by reference. As shown in Figure 3, the device 300 includes a base 301, a drive mechanism 350 coupled to the base 301, a protective housing 302 coupled to the base 301, and a rotatable permeable member 303 disposed within the protective housing 302, and a gas inlet 304 indirectly coupled to the rotatable permeable member 303 (e.g., the gas inlet 304 (which may optionally include a pipe fitting 304a and / or a gas tube fitting 304b) may be indirectly coupled to the rotatable permeable member via a bracket 307, a rotary union 305, and / or a flat plate 308). In some embodiments, device 300 also includes a tube support 306 coupled to rotatable permeable member 303 to reduce or eliminate torsional moments on rotatable permeable member 303. A drive mechanism 350 may provide the rotation. Drive mechanism 350 includes a rotatable component 350a. In some embodiments, drive mechanism 350 is a motor and rotatable component 350a is a rotatable shaft. In some embodiments, drive mechanism 350 is a gear box and rotatable component 350a is a gear shaft.

[0034] The protective housing 302 is defined by a sidewall 302a extending between a first end 302b and a second end 302c. The first end 302b is coupled to the base 301. The protective housing 302 defines a plurality of perforations 302d configured to permit the passage of liquid through the sidewall 302a of the protective housing 302.

[0035] The rotatable permeable member 303 has a body defining a longitudinal axis "X1" and is pivotable about the longitudinal axis X1. The rotatable permeable member 303 is coupled to a rotatable component 350a of the drive mechanism 350 (e.g., a rotatable shaft of a motor, or a gear shaft of a gear box) such that the rotatable permeable member 303 rotates together with the rotatable component 350a of the drive mechanism 350.

[0036] A third embodiment of a suitable nanobubble generator is shown in Figures 4A-4C and is also described in the aforementioned USSN 63 / 150,973, which is incorporated by reference. As shown in Figures 4A-4C, the device 400 includes a housing 401, a permeable member 403, and an electrical conductor 405. The elongated housing 401 is defined by a first end 401a, a second end 401b, and an interior cavity adapted to receive a liquid carrier from a liquid source. The housing 401 includes an inlet and an outlet. The first end 401a may be an inlet and the second end 401b may be an outlet.

[0037] The device 400 includes a gas permeable member 403 at least partially disposed within an interior cavity of a housing 401. The permeable member 403 defines an interior surface, an exterior surface, and a lumen. The permeable member 403 may include a first end 403a adapted to receive pressurized gas from a gas source, a second end 403b, and a porous sidewall 403c extending between the first and second ends 403a, 403b. The first end 403a of the permeable member 403 may be an open end, and the second end 403b of the permeable member 403 may be a closed end. The housing 401 may be coupled to a mount 451, for example, the first end 401a of the housing 401 may be coupled to the mount 451. The mount 451 may provide fluid inlet and / or outlet ports into its coupling components. For example, the mount 451 may define a port 451 a in fluid communication with the first end 403 a of the permeable member 403 .

[0038] The housing 401 and permeable member 403 may be arranged such that as the liquid carrier from the liquid source flows parallel to the outer surface of the permeable member 403 from the liquid inlet to the liquid outlet, the flow velocity of the liquid carrier is greater than a turbulence threshold at which the liquid creates a turbulent flow condition, thereby allowing the liquid to shear gas from the outer surface of the gas permeable member to form nanobubbles in the liquid carrier.

[0039] 4A-C, device 400 includes an electrical conductor 405 in the form of a helical member (e.g., a helical electrode) located within an interior cavity of housing 401. Electrical conductor 405 is adapted to generate a magnetic flux parallel to an outer surface of permeable member 403 as liquid carrier flows from a liquid inlet to a liquid outlet of housing 401. Preferably, electrical conductor 405 is adapted to generate a high frequency oscillating magnetic flux.

[0040] The device 400 may optionally include a hydrofoil 450 shaped to induce rotation in the liquid carrier flowing through the device 400. In some embodiments, the hydrofoil 450 is shaped (e.g., with a tapered and / or curved surface) to induce supercavitation in the liquid carrier flowing through the device 400. For example, the hydrofoil 450 may be shaped to create a region of high turbulence in the fluid flowing through the device 400 based on the surface of the hydrofoil 450 and to create a turbulent trailing edge downstream of the hydrofoil 450. In this disclosure, the terms "downstream" and "upstream" refer to the general direction of flow of the liquid carrier, for example, through the device 400. For example, in Figures 4A-B, the general direction of flow of the liquid carrier through the device 400 is from left to right, so "downstream" correlates to "to the right of" and "upstream" correlates to "to the left of".

[0041] A fourth embodiment of a suitable nanobubble generator is shown in FIG. 5 and is also described in the aforementioned USSN 63 / 150,973, which is incorporated by reference. As shown in FIG. 5, the device 1200 includes a housing 1201 adapted to receive a gas from a gas source, and a gas permeable member 1203 adapted to receive a liquid carrier from a liquid source. The gas permeable member 1203 may be substantially similar to the permeable member 20 (shown in FIG. 2). In the device 1200, a liquid is flowed into the permeable member 1203, and a gas flows around the outer surface of the permeable member 1203. The gas flows through pores into the lumen of the permeable member 1203 to generate nanobubbles that are sheared and dispersed into the liquid flowing through the permeable member 1203.

[0042] The housing 1201 of the device 1200 includes a first end 1201a and a second end 1201b, both of which are closed ends. Gas flows from a gas source through a port 1201c defined by the housing 1201 and into the interior cavity of the housing 1201. Although the port 1201c is shown in FIG. 5 as being located near the center of the housing 1201, it may be located at any point on the housing 1201 so long as it provides an entrance for gas to enter the interior cavity of the housing 1201.

[0043] The permeable member 1203 has a first end 1203a that may serve as a liquid inlet adapted to receive a liquid carrier. The permeable member 1203 includes pores that allow gas to pass through its walls. The permeable member 1203 is enclosed within the interior cavity of the housing 1201 such that gas within the housing flows across the walls of the permeable member 1203. Pressure is applied to force gas through the pores of the permeable member 1203 and into the lumen of the permeable member 1203. Nanobubbles are formed as the gas flows through the pores of the permeable member 1203. As the nanobubbles are formed, the liquid carrier flowing through the lumen of the permeable member 1203 shears the nanobubbles from the inner surface of the permeable member 1203. A second end 1203b of the permeable member 1203 may be an open end or outlet for discharging the liquid carrier carrying the formed nanobubbles.

[0044] 5 includes an electrical conductor 1205 in the form of an electromagnetic coil (e.g., a stator) located on the exterior of the housing 1201. The electrical conductor 1205 surrounds at least a portion of the permeable member 1203 and is located upstream of the port 1201c. As discussed above, the electrical conductor or conductors may be implemented in a variety of ways.

[0045] The device 1200 may optionally include a component (e.g., a helical member and / or a hydrofoil) for inducing rotation in the liquid flowing through the permeable member 1203, as previously described herein. The optional component may be located within an interior cavity of the housing 1201.

[0046] The devices of Figures 1-3, 4A-C, and 5 can each be used to enhance chlorine production through the injection of nanobubbles into a chlorine-containing electrolyte liquid to improve the electrolysis process, as described above. In some embodiments, the chlorine-containing electrolyte liquid is saltwater, and NaCl in the saltwater is decomposed through electrolysis to enhance the production of chlorine gas, or chlorine in its dissolved form. This process can increase the efficiency of chlorine production in saltwater pools, hot tubs, and spas, in desalination plants, and in other industrial processes.

[0047] Although several embodiments of the invention have been described, it will be understood that various modifications can be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.

Claims

1. (a) 1 cm 3 At least 10 per 6 introducing nanobubbles from a nanobubble generator into an electrolytic cell containing a pair of electrodes and a chlorine-containing electrolyte liquid at a concentration of nanobubbles; and (b) operating the electrolytic cell to produce chlorine gas.

16. A method for producing chlorine gas, comprising:

2. 1 cm 3 At least 10 per 7 13. The method of claim 1, comprising introducing the nanobubbles at a concentration of nanobubbles.

3. 1 cm 3 At least 10 per 8 13. The method of claim 1, comprising introducing the nanobubbles at a concentration of nanobubbles.

4. 1 cm 3 At least 10 per 9 13. The method of claim 1, comprising introducing the nanobubbles at a concentration of nanobubbles.

5. 2. The method of claim 1, wherein the nanobubble generator is located within the electrolytic cell.

6. The method of claim 1 , wherein the nanobubble generator is located outside the electrolytic cell.

7. 10. The method of claim 1, wherein the nanobubble generator and the electrolytic cell are located within a common housing.

8. 10. The method of claim 1, further comprising extracting chlorine gas from the electrolytic cell as chlorine gas is produced or after a predetermined time.

9. 9. The method of claim 8, further comprising the step of delivering chlorine gas from the electrolytic cell to a chlorine application.

10. the electrolytic cell further produces oxygen gas; the method further comprising extracting oxygen gas from the electrolytic cell as the oxygen gas is produced or after a predetermined time; 2. The method of claim 1.

11. The nanobubbles may be air, nitrogen, carbon dioxide, or NO X 2. The method of claim 1, wherein the tank is filled with a gas selected from the group consisting of toluene, methane, and combinations thereof.

12. 10. The method of claim 1, wherein the chlorine-containing electrolyte liquid comprises water.

13. 10. The method of claim 1, wherein the chlorine-containing electrolyte liquid comprises ammonia.

14. 10. The method of claim 1, wherein the chlorine-containing electrolyte liquid comprises wastewater.

15. The nanobubble generator comprises: (a) an elongated housing having a first end and a second end, the housing defining a liquid inlet, a liquid outlet, and an interior cavity adapted to receive a liquid carrier from a liquid source; (b) a gas permeable member at least partially disposed within the interior cavity of the housing, the gas permeable member having an open end adapted to receive pressurized gas from a gas source, a closed end, and a porous sidewall extending between the open end and the closed end, the gas permeable member defining an interior surface, an exterior surface, and a lumen. Equipped with the housing and gas permeable member are configured such that as the liquid carrier from the liquid source flows parallel to the outer surface of the gas permeable member from the liquid inlet to the liquid outlet, a flow velocity of the liquid carrier is greater than a turbulence threshold at which the liquid creates a turbulent flow condition, thereby allowing the liquid to shear gas from the outer surface of the gas permeable member to form nanobubbles in the liquid carrier.

2. The method of claim 1.

16. The nanobubble generator comprises: at least one electrical conductor adapted to generate a magnetic flux parallel to an outer surface of the gas permeable member as the liquid carrier flows from the liquid inlet to the liquid outlet; 16. The method of claim 15, further comprising:

17. 17. The method of claim 16, wherein the gas permeable member is electrically conductive.

18. The method of claim 16 , wherein the electrical conductor comprises an electromagnetic coil.

19. The nanobubble generator comprises: a helical member adapted to rotate the liquid carrier as it flows from the liquid inlet to the liquid outlet.

17. The method of claim 15 or 16, comprising:

20. The nanobubble generator comprises: a helical member adapted to rotate the liquid carrier as it flows from the liquid inlet to the liquid outlet. Equipped with The helical member is an electromagnetic coil adapted to generate a magnetic flux parallel to an exterior surface of the gas permeable member as the liquid carrier flows from the liquid inlet to the liquid outlet. Equipped with 17. The method of claim 15 or 16.

21. 17. The method of claim 15 or 16, wherein the nanobubble generator further comprises a hydrofoil located within the interior cavity of the housing.

22. The nanobubble generator comprises: a motor having a rotatable shaft; a pivotable permeable member including a body having a wall and a plurality of pores through which a gas introduced into the pivotable permeable member can flow, the pivotable permeable member being connectable to a gas inlet configured to introduce gas from a gas source into the pivotable permeable member, the pivotable permeable member adapted to be connected to and rotate with the rotatable shaft of the motor; and a rotatable tube support including an elongated body having a wall and defining an internal cavity; the wall defining a plurality of perforations; the internal cavity of the rotatable tube support configured to house the pivotable permeable member; the rotatable tube support coupled to and rotatable with the rotatable shaft of the motor; the rotatable tube support adapted, upon rotation, to introduce the liquid into the internal cavity of the rotatable tube support and to move the liquid away from an outer surface of the body of the rotatable permeable member; the pivotable permeable member adapted, upon rotation, to simulate turbulence in the liquid above a turbulence threshold, the turbulence enabling the liquid to shear gas from the outer surface of the pivotable permeable member thereby forming nanobubbles in the liquid; 2. The method of claim 1, comprising:

23. The nanobubble generator comprises: (a) an elongated housing having a first end and a second end, the housing further comprising an internal cavity and a gas inlet adapted to introduce pressurized gas from a gas source into the internal cavity; (b) a gas permeable member at least partially disposed within the interior cavity of the housing, the gas permeable member including a liquid inlet adapted to receive liquid from a liquid source, a liquid outlet, and a porous sidewall extending between the liquid inlet and the liquid outlet, the gas permeable member defining an inner surface, an outer surface, and a lumen through which liquid flows; (c) at least one electrical conductor adapted to generate a magnetic flux parallel to the inner surface of the gas permeable member as a liquid carrier flows from the liquid inlet to the liquid outlet. Equipped with the housing and gas permeable member are configured such that as the liquid carrier from the liquid source flows from the liquid inlet to the liquid outlet parallel to the inner surface of the gas permeable member, a flow velocity of the liquid carrier is greater than a turbulence threshold at which the liquid creates a turbulent flow condition, thereby allowing the liquid to shear gas from the inner surface of the gas permeable member to form nanobubbles in the liquid carrier.

2. The method of claim 1.

24. (a) 1 cm 3 At least 10 per 6 A nanobubble generator capable of generating nanobubbles; and (b) an electrolytic cell having a pair of electrodes and in communication with the nanobubble generator; Equipped with The electrolytic cell is capable of generating chlorine gas from a chlorine-containing electrolytic liquid. An apparatus for producing chlorine gas.

25. a chlorine application destination in communication with the electrolytic cell, the chlorine application destination having an inlet for receiving chlorine gas from the electrolytic cell; 25. The apparatus of claim 24, further comprising:

26. (a) 1 cm 3 At least 10 per 6 introducing nanobubbles from a nanobubble generator into an electrolytic cell containing a pair of electrodes and an electrolytic liquid at a concentration of nanobubbles; and (b) operating the electrolytic cell to produce one or more electrolysis products.

23. A method for producing an electrolysis product comprising:

27. 27. The method of claim 26, wherein the electrolytic liquid is a chlorine-containing electrolytic liquid.

28. 27. The method of claim 26, wherein the electrolytic liquid is a hydrogen-containing electrolytic liquid.

29. 27. The method of claim 26, wherein the one or more electrolysis products include chlorine gas.

30. 27. The method of claim 26, wherein the one or more electrolysis products include hydrogen gas.

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